US3372155A - Mixed chromium complex monoazo dyestuffs - Google Patents
Mixed chromium complex monoazo dyestuffs Download PDFInfo
- Publication number
- US3372155A US3372155A US347386A US34738664A US3372155A US 3372155 A US3372155 A US 3372155A US 347386 A US347386 A US 347386A US 34738664 A US34738664 A US 34738664A US 3372155 A US3372155 A US 3372155A
- Authority
- US
- United States
- Prior art keywords
- hydroxynaphthalene
- aminophenol
- parts
- dyestuffs
- nitro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052804 chromium Inorganic materials 0.000 title claims description 21
- 239000011651 chromium Substances 0.000 title claims description 21
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 15
- 239000000975 dye Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 12
- -1 4-nitro-2-aminophenol 1-methyl-sulfonylamino-7- hydroxynaphthalene Chemical compound 0.000 description 11
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 210000002268 wool Anatomy 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 8
- ALNWQAFPXMGLTJ-UHFFFAOYSA-N n-(7-hydroxynaphthalen-1-yl)acetamide Chemical compound C1=C(O)C=C2C(NC(=O)C)=CC=CC2=C1 ALNWQAFPXMGLTJ-UHFFFAOYSA-N 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- 240000007817 Olea europaea Species 0.000 description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- SWFNPENEBHAHEB-UHFFFAOYSA-N 2-amino-4-chlorophenol Chemical compound NC1=CC(Cl)=CC=C1O SWFNPENEBHAHEB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- DOPJTDJKZNWLRB-UHFFFAOYSA-N 2-Amino-5-nitrophenol Chemical compound NC1=CC=C([N+]([O-])=O)C=C1O DOPJTDJKZNWLRB-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JMSFXRZVVNHDDC-UHFFFAOYSA-N n-(7-hydroxynaphthalen-1-yl)benzamide Chemical compound C12=CC(O)=CC=C2C=CC=C1NC(=O)C1=CC=CC=C1 JMSFXRZVVNHDDC-UHFFFAOYSA-N 0.000 description 2
- CPANFUIQOQQIGG-UHFFFAOYSA-N n-(7-hydroxynaphthalen-1-yl)methanesulfonamide Chemical compound C1=C(O)C=C2C(NS(=O)(=O)C)=CC=CC2=C1 CPANFUIQOQQIGG-UHFFFAOYSA-N 0.000 description 2
- FZCQMIRJCGWWCL-UHFFFAOYSA-N 2-amino-5-chlorophenol Chemical compound NC1=CC=C(Cl)C=C1O FZCQMIRJCGWWCL-UHFFFAOYSA-N 0.000 description 1
- NFNLMGYLSDEJKS-UHFFFAOYSA-N 3-amino-4-hydroxy-n-methylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(O)C(N)=C1 NFNLMGYLSDEJKS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DFPNOBYKTMZUIK-UHFFFAOYSA-N n-(7-hydroxynaphthalen-1-yl)propanamide Chemical compound C1=C(O)C=C2C(NC(=O)CC)=CC=CC2=C1 DFPNOBYKTMZUIK-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/16—Monoazo compounds containing chromium
Definitions
- the present invention relates to a group of unique mixed chromium complex azo dyestuffs, and to an improved process for the preparation of the same.
- the invention is based, at least in part, on the discovery that valuable mixed chromium complex azo dyestuffs may be produced by reacting chromium-yielding agents with a mixture of monoazodyestuifs of the formulae:
- a and B represent radicals of the diazo components, preferably radicals of the benzene series, in each of which the substituen-ts X and X are in the o-position to the azo grouping;
- X and X represent metal complex-forming groups or such substituents which are transformed into metal complex-forming groups under metallizing conditions,
- R represents an alkylsulfonyl or arylsulfonyl group, and R represents an acyl radical different from that represented by R.
- X represents a hydroxyl or alkoxy group
- Y and Y represent hydrogen or non-ionic substituents
- in and n are the integers 1 or 2
- R represents an alkylsulfonyl or arylsulfonyl group
- R represents an alkylsulfonyl or arylsulfonyl group different from that represented by R or for the acyl radical of an aliphatic or aromatic carboxylic acid.
- the monoazodyestuifs I and III utilized in the process of the invention differ from each other at least with respect to the tape of their acyl substituent R or R If, in both cases alkylsulfonyl or arylsulfonyl radicals are present, they must not, by definition, be identical.
- the difference between the acyl radicals R and R may also be due to the fact that R is derived from an aliphatic or aromatic sulfonic acid, whereas R is derived from an aliphatic or aromatic carboxylic acid.
- a particularly desirable dyestulf of this invention comprises the mixed chromium complex azo dyestulf which contains in complex union one atom of chromium and two molecules of different monoazo dyestuffs of the formulae:
- Z stands for methyl, ethyl, or phenyl
- Z stands for methyl, ethyl, phenyl, or p-methylphenyl
- the diazo compounds in dyestuffs I and II may be identical or different in constitution. Preferably, however, they belong to the benzene series. If the diazo components are further substituted, nonionic constituents are preferred in many cases as, for example, alkyl, alkoxy, nitro, etc., and optionally further substituted sulfonarnido, sulfone, acylamino and halogen substituents.
- the preferred dyestuffs to .be used in the process of the invention are those represented by Formulae III and IV. Naturally, dyestuffs with acid, water-solubilizing groups such as sulfonic acid, and not complex-linked carboxylic acid groups may also be used in practicing the process of the invention.
- metal complex-forming groups X and X which in the radicals A and B stand in an adjacent position to the azo group, hydroxy or alkoxy groups are to be considered preferred. Additionally, the carboxylic acid group is also entirely satisfactory for this purpose.
- Substituents capable of being transformed into metal complex-linked groups under 'rnetallizing conditions include, for example, SO H and CI.
- the monoazodyestuffs which may be used in the process of the invention are, for example:
- 2-aminophenol-4-sulfonamide-e 1-methyl-sulfonylamino-7- hydroxynaphthalene; 2-aminophenol-4-sulfomethylamide l-methyl-sulfonylamino-7-hydroxynaphthalene; 2-aminophenol-4-sulfodimethyl-amide+ l-methylsulfonylamino-7-hydroxynaphthalene; 2-aminophenol-4-methylsulfone l-methylsulfonylamino- 7-hydroxynapththalene; 2-aminophenol-4-ethylsulfone- 1-methylsulfonylamino-7- hydroxynaphthalene', Z-aminophenol-S-sulfoamidee l-methyl-sulfonylamino-7- hydroxynaphthalene; Z-aminophenol-S-rnethyl-sulfonel-methyl-sulfonylamino-7-hydroxyna
- monoazodyestuffs II or IV there may be used, among others:
- Preparation of those monoazo dyestuffs may be effected by known techniques such as by coupling the diazo component listed initially in each case (i.e., preceding the arrow) within, preferably, an aqueous alkaline medium with the coupling component listed secondly in each case (i.e., following the arrow).
- various methods are known from prior literature sources. Especially advantageous are those methods which are carried out at temperatures within the range of from 100-15() C.
- reaction of the lzl-complex compounds with the metal-free monoazo dyestuffs takes place in an aqueous, organic-aqueous or organic medium in the weakly acid, neutral or, preferably, weakly alkaline range.
- chroming methods are used, mostly within an alkaline medium, which, according to experience yield Zzl-complex compounds.
- Such methods include, for example, the
- dyestuffs I and ll which is occasionally desirable in order to produce certain color shades.
- mixtures of more than one each of the dyestuffs represented by Formulae I and II may be employed.
- metallizable azo dyestuffs of a different basic structure as, for example, those which are synthesized from diazo components of the benzene or naphthalene series and phenolic coupling components other than 1-acylamino-7-hydroxynaphthalene such, for example, from diazo components of the benzene series with o-positioned hydroxy, alkoxy or carboxy groups and l-hydroxy-5,8-dichloroor -dibromonaphthalene; 2-hydroxynaphthalene; 2-hydroxynaphthalene-3,6-disulphonic acid amides; 1-hydroxy-4-alkylnaphthalenes; 4' hydroxynaphtho-(2',1' :4,5)-oxathiol S-dioxide, and others.
- metallizable monoazo dyestuffs which are obtained from diazo components of the benzene series with a hydroxyl, alkoxy, or carboxy group in o-position, and enolic coupling components, such as acylacetic acid amides, especially aryl amides, S-pyrazolones, particularly 1-aryl-3-methyl-5- pyrazolones, or S-amino pyrazoles, especially 1-aryl-3- methyl-S-aminopyrazoles.
- Dyestuffs of this type are known in large numbers from the prior literature available on chromium complex azo dyestuffs.
- metal complex-forming azo dyestuffs other metal complex-forming dyestuffs, such as azomethine dyestuffs or the like, may, of course, be used for the mixed chroming as additional metallizable dyestulf components.
- the new mixed chromium complex azo dyestufis of the invention are readily water-soluble in the form of their alkali metal salts. They are efiective in dyeing wool and materials of similar dye receptivity, such as silk, leather, synthetic polyamide and polyurethane fibers, in very fast, level colors, fast to rubbing. In dyeing wool, for example, dyeing techniques in weakly acid (organic acid) as well as in neutral baths are very suitable.
- Example I The monoazo dyestuff 4-nitro-2-aminophenol l-methyl-sulphonylamino-7-hydroxynaphthalene, in amount of 40.2 parts by weight (obtained according to the method of German Patent No. 951,749), was stirred in 600 parts by volume of ethylene glycol; 266 parts by weight of O 21? C 1138 O 2-HN 9 NHOCCH: NO:
- Example 2 The monoazo dyestuff 4-nitro-2-aminophenol l-methylsulphonylamino-7-hydroxynaphthalene, in amount of 40.2 parts by weight, and 36.6 parts by weight of the monoazo dyestuff 4nitro-2-aminophenyl 1-acetyl-amino- 7-hydroxynaphthalene were well stirred with 3500 parts by volume of water at 95 C., and dissolved by the addition of 23 parts by Volume of a 40% by volume sodium hydroxide solution. Directly afterwards a solution of 17.8 parts by weight of sodium dichromate (Na Cr O 2H O) and 16.3 parts by weight of grape sugar in 210 parts by volume of water and 85 parts by volume of ammonia Water (25%) were run in the mixture.
- Example 3 into 4500 parts by volume of water. By dropping in 670 parts by weight of rock salt the mixed chromium complex dyestuif was separated. After filtering-off by suction and drying, a dark powder was obtained which dyed wool from an organic acid to neutral bath in fast and level blue-grey shades.
- Example 4 The monoazo dyestuff 2-aminophenol-4-sulphonamide 1-methyl-sulphonylamino 7 hydroxynaphthalene, in amount of 43.6 parts by weight, was stirred into 600 parts by volume of ethylene glycol, 26.6 parts by weight of crystaline chromic chloride were added and the mixture heated, while stirring, to 125130 C. for 4 hours. It was then allowed to cool to 110 C. and 40.0 parts by weight of the monoazo dyestufi 2-amino-phenol-4-sulphonamide 1-acetylamino-7-hydroxynaphthalene and 150 parts by volume of formarnide were added. The reaction solution was stirred for 60 minutes at 100 C.
- Example 5 The monoazo dyestuif 2-aminophenol-4-sulphonamide 1-methyl-sulph0nylamino 7 hydroxynaphthalene, in amount of 43.6 parts by weight, was transformed into the lzl-chrdomium complex dyestuff as described in Example 4. The chroming mixture was allowed to cool to C., and then 36.6 parts by weight of the monoazo dyestuff 4-nitro-2-aminophendle l-acetylamino 7 hydroxynaphthalene and parts by volume of formamide were added and the mixture was stirred for a further 60 minutes at 100 C. The reaction mixture was then poured into 4000 parts by volume of water. In order to se arate the dyestuif, 600 parts by weight of rock salt were dropped into the mixture which was filtered by suction. After drying, a. black powder was obtained which dyed wool from an organic acid to neutral bath in fast and level gray shades.
- Example 6 The monoazo dyestuff 4-nitro-2-aminophenol+ l-methylsulphonylamino-7-hydroxynaphthalene, in amount of 40.2 parts by weight; 36.6 parts by weight of the monoazo dyestufi 4-riitro 2 aminophenol 1-acetylamino-7-hydroxynaphthalene, and 37.6 parts by weight of the monoazo dyestuff 2-aminophenol-4-sulphonamideacetoacetic acid anilide were stirred with 4500 parts by volume of water, heated to 95 C. and dissolved by the addition of 35 parts by volume of a 40% by volume sodium hydroxide solution.
- the mixtures of two metal-free dyestuffs of the following list for chroming the mixture, or the 1:1-chromium complex of the one monoazo dyestuif for reaction with the other metal-free monoazo dyestuff, mixed 2: l-chromium complex dyestuffs are obtainable which exhibit likewise very good fastness properties and which dye wool in the shades mentioned below.
- the dyestufl having the formula: 1.
- a mixed chromium complex azo dyestufi which con- 9 tains in complex union one atom of chromium and two N02 HaCOzSHN- molecules of different monoazo dyestuffs of the formulae:
- N N OH OH Cr Na.
- Z stands for methyl, ethyl, or phenyl
- Z CHARLES PARKER Primary Examiner stands for methyl, ethyl, phenyl, or p-methylphenyl.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0039137 | 1963-02-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3372155A true US3372155A (en) | 1968-03-05 |
Family
ID=7097641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US347386A Expired - Lifetime US3372155A (en) | 1963-02-28 | 1964-02-26 | Mixed chromium complex monoazo dyestuffs |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3372155A (en)) |
| BE (1) | BE644415A (en)) |
| CH (1) | CH466462A (en)) |
| DE (1) | DE1444658A1 (en)) |
| GB (1) | GB1028236A (en)) |
| NL (1) | NL6401932A (en)) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522231A (en) * | 1965-11-22 | 1970-07-28 | Geigy Ag J R | Asymmetrical 1:2 chromium complex azo dyestuffs |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2610175A (en) * | 1949-11-18 | 1952-09-09 | Ciba Ltd | Complex chromium compounds of monoazo-dyestuffs |
| CH334634A (de) * | 1954-01-16 | 1958-12-15 | Bayer Ag | Verfahren zur Herstellung von Monoazofarbstoffen |
| CA637049A (en) * | 1962-02-20 | Ciba Limited | Metalliferous azo-dyestuffs |
-
1963
- 1963-02-28 DE DE19631444658 patent/DE1444658A1/de not_active Ceased
-
1964
- 1964-01-28 CH CH96264A patent/CH466462A/de unknown
- 1964-02-26 US US347386A patent/US3372155A/en not_active Expired - Lifetime
- 1964-02-27 NL NL6401932A patent/NL6401932A/xx unknown
- 1964-02-27 BE BE644415D patent/BE644415A/xx unknown
- 1964-02-27 GB GB8209/64A patent/GB1028236A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA637049A (en) * | 1962-02-20 | Ciba Limited | Metalliferous azo-dyestuffs | |
| US2610175A (en) * | 1949-11-18 | 1952-09-09 | Ciba Ltd | Complex chromium compounds of monoazo-dyestuffs |
| CH334634A (de) * | 1954-01-16 | 1958-12-15 | Bayer Ag | Verfahren zur Herstellung von Monoazofarbstoffen |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522231A (en) * | 1965-11-22 | 1970-07-28 | Geigy Ag J R | Asymmetrical 1:2 chromium complex azo dyestuffs |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1028236A (en) | 1966-05-04 |
| DE1444658A1 (de) | 1969-02-27 |
| BE644415A (en)) | 1964-06-15 |
| CH466462A (de) | 1968-12-15 |
| NL6401932A (en)) | 1964-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2610175A (en) | Complex chromium compounds of monoazo-dyestuffs | |
| US2933489A (en) | Heavy metal-containing dyestuffs | |
| US2778816A (en) | Cobaltiferous and chromiferous azo-dyestuffs | |
| US3005813A (en) | Metalliferous azo-dyestuffs | |
| US2734895A (en) | Cochj | |
| US3040019A (en) | Metal-complex dyestuffs | |
| US3221003A (en) | Chrgmium cqmplex mixed azo dyestuffs | |
| US2901473A (en) | Oxazoline and dihydro oxazine monoazo dyestuffs and their metal complex compounds | |
| US2839521A (en) | Azo dyestuffs containing heavy metal | |
| US2804454A (en) | Complex heavy metal compounds of monoazo dyestuffs | |
| US3372155A (en) | Mixed chromium complex monoazo dyestuffs | |
| US3067191A (en) | chschohchaoh | |
| US2749332A (en) | Metalliferous azo-dyestuffs | |
| US2856397A (en) | Production of metal-containing azo dyestuffs | |
| US4996303A (en) | Preparation of 1:2 metal complex dyes by coupling in the presence of a metal donor in an inert gas atmosphere | |
| US2832760A (en) | Cooh i | |
| US2479944A (en) | Metallized benzimidazole azo dyestuffs | |
| US2832762A (en) | Monoazo dyestuffs and complex metal compounds thereof | |
| US2849436A (en) | Metalliferous monoazo-dyestuffs and process of making same | |
| US3970615A (en) | Unsymmetrical mono-sulfo containing chromium complexes of azo dyes | |
| US2817657A (en) | Cobaltiferous monoazo-dyestuffs | |
| US3925346A (en) | Mixed chromium-containing azo dyestuffs containing, per atom of chromium, one molecule of an o,o'-dihydroxy-sulphophenylene-azo-naphthalene and one molecule of an -o-hydroxyphenylene-azo-acetoacetamide | |
| US2784179A (en) | Metalliferous azo-dyestuffs | |
| US2969350A (en) | Azo dyestuffs and their metal complex compounds | |
| US2814615A (en) | Soinhi |